JPS59130377A - Leather-like product comprising ethylene copolymer filled with cellulosic filler - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to early fall products, and more particularly the present invention relates to early fall products obtained from wood-filled ethylene copolymers (interpolymers).

U.S. Pat. No. 4,191,798 essentially describes a
50% of at least one copolymer of ethylene and at least one comonomer, such as vinyl esters of saturated carboxylic acids, unsaturated mono- or dicarboxylic acids, and esters of unsaturated mono- or dicarboxylic acids: (b
) about 2% to 15% by weight process oil; and (C) about 50% to 90% by weight fillers such as calcium carbonate and barium sulfate. A thermoplastic composition is disclosed.

European Patent Specification No. 13089 to Stead et al. discloses the use of a blend of ethylene/propylene copolymer and 40% wood flour in a laminate with fabric.

Yagi Japanese Patent No. 79-92613 discloses a blend of atactic polypropylene with a mixture of calcium carbonate, ammonium phosphate and wood flour.

Japanese Patent Publication No. 76-69552 of Nahano et al.
Blends containing ~45% polyolefin, less than 50% powdered wood, and less than 50% calcium carbonate are disclosed.

U.S. Patent Application No. 273,418 filed June 15, 1981
No. 5 to 55% by weight of ethylene/alpha-olefin copolymers, alpha-olefins containing 4 to 10 carbon atoms; about 2 to 12% by weight of process oils, epoxidized oils, polyesters , a plasticizer selected from the group consisting of polyethers and polyether esters, with a dual weight of about 40
~90%, e.g. calcium carbonate, barium sulfate,
Filled thermoplastics useful as sound insulation sheets for automotive carpets obtained by blending hydrated alumina, silica, fly ash, cement dust, wood flour, rice husk flour and mixtures thereof; and optionally elastomeric polymers. A composition is disclosed.

U.S. Patent Application No. 273,419 filed June 15, 1981
5-55% by weight of ethylene copolymers, such as ethylene/vinyl acetate, ethylene/unsaturated mono- or dicarboxylic acids or esters of said unsaturated acids; % of a plasticizer selected from the group consisting of polyesters, polyethers, polyether esters and their combinations with process oils; , fillers such as magnesium carbonate, calcium sulfate, silica, fly ash, cement dust, wood flour, rice husk flour and mixtures thereof; and optionally, for example, unvulcanized elastomeric polymers and certain additives thereof. Discloses filled thermoplastic compositions useful, for example, as acoustic sheeting for car carpets, obtained by blending modified resins, such as homopolymers and copolymers of ethylene and propylene. There is.

U.S. Patent Application No. 273,420 filed June 15, 1981
A mixture of copolymers of at least 2 seconds of ethylene with a specified polar comonomer content of about 5-55% by weight; e.g. calcium carbonate, barium sulfate, hydrate, about 40-90% by weight Fillers such as alumina, clay, magnesium carbonate, calcium sulfate, silica, fly ash, cement dust, wood flour, rice husk flour and mixtures thereof; and 0-15% by weight of process oil, polyester, a plasticizer selected from the group consisting of ethers and polyether esters; and optionally obtained by blending, for example, elastomeric polymers and certain other modified resins, such as small mobolymers and copolymers of ethylene and propylene. be done,
10 - Discloses filled thermoplastic compositions useful as acoustical sheets with improved tensile elongation.

In accordance with the present invention, (a) from about 5 to about 55% by weight;
vinyl esters of ethylene and saturated carboxylic acids in which the acid moiety has up to 4 carbon atoms; unsaturated mono- and dicarboxylic acids with 3 to 5 carbon atoms; at least one comonomer selected from the group consisting of esters of unsaturated acids and alpha-olefins containing from 4 to 10 carbon atoms.
species copolymer, the ethylene content of the copolymer being about 4 by weight.
0 to about 95%, the comonomer content of the copolymer is about 5 to about 60% by weight, and! The melt index of the a polymer is from about 0.1 to about 150 q/10 min, provided that when the copolymer of ethylene is an ethylene/vinyl ester or an ethylene/unsaturated mono- or dicarboxylic acid ester, the copolymer The combination can contain up to about 15% by weight carbon monoxide; (b) from 1 to about 15% by weight from the group consisting of process oils, epoxidized oils, polyesters, polyethers, and polyether esters; (C) about 20 to about 70% by weight of a cellulose filler; (d) 0 to about 10% by weight of an organic acid, an organic acid derivative, and a surfactant; at least one additive selected from the group consisting of:

Further in accordance with the present invention there is provided extruded sheets or films and injection molded articles having a hanging appearance comprising the compositions of the present invention.

In accordance with the invention there is further provided a temporary structure having a suspended appearance, comprising at least one composition of the invention bonded to a hard and/or soft substrate.

The use of cellulose fillers, such as wood flour, in combination with certain plasticized ethylene copolymers can give compositions that can be processed into products that significantly resemble leather. discovered.

The term "hung" refers to characteristics of appearance, surface texture, and flexibility. Moreover, the compositions of the present invention can be easily processed using thermoplastic processing methods.

Ethylene copolymers suitable for the shaped products of the invention are:
Vinyl esters of saturated carboxylic acids in which the acid moiety has up to 4 carbon atoms, unsaturated mono- or dicarboxylic acids with 3 to 5 carbon atoms, salts of such unsaturated acids, and alcohol moieties from 1 to 8 carbon atoms. and at least one comonomer selected from the group consisting of esters of said unsaturated acids having Terpolymers of ethylene and the comonomers mentioned above are also suitable. Ionomers, which are fully or partially neutralized copolymers of ethylene and the above-mentioned acids, are described in further detail in US Pat. No. 3,264,272. In addition, ethylene/vinyl acetate/-carbon oxide, ethylene/acrylic acid containing up to about 15% carbon monoxide by weight
Terpolymers of -butyl/'-carbon oxide or ethylene 7/methyl acrylate/-carbon oxide can also be used. Suitable comonomers are the vinyl esters of saturated carboxylic acids and esters of unsaturated carboxylic acids mentioned above.

The ethylene content of the copolymer is about 40 to 95% by weight, preferably about 45 to about 90% by weight, and most preferably about 60 to about 85% by weight.

The comonomer content is about 5% to 60% by weight, preferably about 10% to about 55% by weight, and most preferably about 1% by weight.
5 to about 40%. Instead of a single copolymer, mixtures of 21 or more ethylene copolymers can be used in these blends, as long as the average value for the comonomer content is within the ranges specified above. In particular, June 1981, the disclosure of which is incorporated herein by reference.
Mixtures such as those described and claimed in US patent application Ser.

The copolymer has a melt index of about 0.1 to about 150.
(+/10 minutes, preferably about 0.3 to about 50 (J/1
0 minutes, but preferably about 0.7 to about 10 (1/1
It is 0 minutes.

According to the above, suitable ethylene copolymers include ethylene/
Vinyl acetate, ethylene/acrylic acid and its ionomer, ethylene/methacrylic acid and its ionomer, ethylene/methyl acrylate, ethylene/ethyl acrylate, ethylene/isobutyl acrylate, ethylene/n-butyl acrylate, ethylene/isobutyl acrylate /
Methacrylic acid and its ionomer, ethylene/n-butyl acrylate/methacrylic acid and its ionomer,
Ethylene/isobutyl acrylate/acrylic acid and its ionomer, ethylene/n-butyl acrylate/acrylic acid and its ionomer, ethylene/methyl methacrylate, ethylene/vinyl acetate/methacrylic acid and its ionomer, ethylene/vinyl acetate/-oxidation Carbon, ethylene/methyl acrylate/-carbon oxide, ethylene,/
n-butyl acrylate/-carbon oxide, ethylene/isobutyl acrylate/-carbon oxide, ethylene/vinyl acetate/
Includes monoethyl maleate and ethylene/methyl acrylate/monoethyl maleate.

Particularly suitable copolymers are ethylene/vinyl acetate, ethylene 7/ethyl acrylate, ethylene/methyl acrylate,
Includes ethylene/isobutyl acrylate, ethylene/n-butyl acrylate, and ethylene/methyl methacrylate copolymers.

Also suitable for the practice of the invention are linear copolymers of ethylene and at least one α-olefin comonomer selected from the group consisting of α-olefins containing 4 to 10 carbon atoms. Preferably, the comonomer contains 4 to 8 carbon atoms. The ethylene-alpha-olefin copolymers of the compositions of the present invention are generally prepared using a transition die catalyst at a synthesis pressure of 5000 psi with no vortex.

Suitable methods for making 1 m of these copolymers are detailed in US Pat. No. 4,076,698 and US Pat. No. 4,163,831.

The ethylene content of the copolymer is about 75 to about 98% by weight and the alpha-olefin comonomer content is about 2 to about 25% by weight. Preferred ethylene and comonomer contents are about 80 to about 96% by weight and about 4% by weight, respectively.
20% to about 20%.

Mixtures of two or more ethylene copolymers can also be used in the blends of the invention instead of a single copolymer, as long as the α-olefin comonomer content (expressed in weight percent) of the mixture is within the ranges mentioned above. The most preferred comonomer content is from about 6% to about 16% by weight. Within this range, the blend exhibits a combination of tensile properties and flexibility useful in the practice of this invention. Relatively stiff blends can be obtained by lowering the comonomer content in the copolymer below about 6% by weight.However, as the comonomer content is lowered, elongation decreases and the plasticizer Compatibility problems may occur.Comonomer contents higher than 16% by weight give blends with relatively low stiffness and relatively low tensile strength, but their elongation is reduced.

Generally, in the rod-shaped products of the present invention, from about 5 to about 55% by weight.
ethylene copolymer is used. Preferably about 1 by weight
0 to 50% ethylene copolymer is used, most preferably about 15 to about 30% by weight.

The first group of plasticizer components of the rods of this invention are known as processing oils. Three types of processing oils are known: paraffinic, aromatic and naphthenic. None of these are pure (grades indicate the main types of oils present.

Process oils are also subdivided by viscosity range.

"Thin" oil is 100'F (38°C)
It has a low viscosity such as 18- and 100 to 500 SUS (Saybolt Universal Second). ""heavy oil °' is 1
It has a high viscosity such as 600O8US at 00A (38°C). Processing oils having a viscosity of about 100 to 6000 SUS at 100"F (38C) are preferred, especially naphthenic and aromatic oils.

In selecting a process oil, factors other than the type of oil selected and its viscosity must be considered. These are described in detail in US Pat. No. 4,191,798, the disclosure of which is incorporated herein by reference.

A second group of plasticizers useful in the practice of this invention is the group consisting of epoxidized oils, such as epoxidized soybean oil and epoxidized linseed oil.

A third group of effective plasticizers are liquid condensates of polybasic acids and polyols. The term "liquid-like" in the context of the present invention is used to mean pourable at room temperature. The acid component is most often a saturated aliphatic dibasic acid or an aromatic dibasic acid, with adipic acid, azelaic acid, phthalic acid, sepacic acid and glutaric acid, or mixtures thereof being commonly used. The polyols can be aliphatic bolanols or polyoxyalkylene polyols, such as ethylene glycol, propylene glycol, 1,4- and 1,3-butene glycol, diethylene glycol and polyethylene glycol. A preferred polyester composition comprises an acid component of which 50% by weight is a group dibasic acid and a polyol component of an aliphatic polyol, more preferably an aliphatic glycol. The most preferred compositions are those based on adipic or azelaic acid and propylene glycol or 1,3- or 1,4-butane glycol. The molecular weight of these plasticizers can vary from as low as a few hundred to as high as about 10,000. The molecular weight of commercially available products is rarely specified. Commercial trade commonly categorizes products into low, medium, or high molecular weight ranges. The preferred range for the purposes of the present invention falls into the middle category.

Mixtures of polyester and hydrocarbon oils are also useful plasticizers in this invention. One purpose of using such mixtures is to combine the high efficiency of relatively expensive polyesters with the low cost of hydrocarbon oils. The price/performance of formulations plasticized with such mixtures may vary for specific applications, as properties can be more precisely tailored or filler content can be increased. It can be greatly improved.

Distinct classes of plasticizers, namely polyethers and polyetheresters, are also useful plasticizers in the strip products of this invention. Generally, polyethers are oligomers or polymers of alkylene oxides, with ethylene or polyethylene oxide polymers being the most common commercially available! It is class I. Polyethers can be produced, for example, by polymerization of aldehydes using various catalysts or by polymerization of alkylene oxides using acid or base catalysts. Polyethers can be end-terminated with hydroxyl groups to form diols (glycols) or, in the case of adducts of alkylene oxide and glycerin, e.g. triols, and so on.

Hydroxyl-terminated polyethers can also be reacted with acids to form esters. Fatty acids such as lauric acid and stearic acid are commonly used. The most common examples of these compounds are mono- and diesters of polyethylene or polypropylene glycol. The intermolecular range of the polyether can range up to the values typical for high polymers.

Preferred polyether compositions in the practice of this invention are those comprising poly22-ols based on random and/or block copolymers of ethylene oxide and propylene oxide. Copolymer polyols offer better performance in terms of efficiency in the formulations of the invention with very high filler content.

Mixtures of polyether or polyether ester plasticizers and polyester plasticizers or hydrocarbon processing oils can also be used in the practice of this invention. The advantage of using a polyether/polyester combination is a reduction in price since polyether is cheaper than polyester. The combination of polyether and process oil is also relatively inexpensive due to the low cost of process oils.

The amount of plasticizer, such as processing oil, present in the suspended product of the present invention is from 1 to about 15% by weight, preferably from about 2 to about 12% by weight. Most preferably, the amount of plasticizer is from about 3% to about 8% by weight.

The third essential component of the rod-shaped product of the present invention is a filler. Suitable fillers include, for example, soft and hard wood flour, wood fibers,
Cellulosic fillers such as sawdust, corn cobs, rice husk flour, and flours such as peanut flour and walnut flour, and optionally with these fillers, such as calcium carbonate, barium sulfate, hydrated alumina, It is a mixture with inorganic fillers such as clay, magnesium carbonate, calcium sulfate, silica, fly ash and cement dust. Suitable fillers are soft and hard flours and mixtures thereof with the above-mentioned inorganic fillers.

The amount of filler present in the suspended product of the present invention is approximately 2 by weight.
0 to about 70%, preferably about 45 to about 70% by weight
It is.

In addition to the above-mentioned components, the rod-shaped product of the present invention can also contain other additives in order to obtain certain properties. Among these additives, suitable types of kRM
can be mentioned. Organic acids encompass a wide range of saturated acid classes ranging from C6-based saturated carboxylic acids such as caproic acid to long chain ones such as C2t (behenic acid). Fatty acids are very effective at increasing elongation and increasing melt index at very low tides. This generally results in a decrease in the stiffness of the blend. In addition to monomeric organic acids, so-called "dimeric" and trimer acids (simpler linear forms of dimers and trimers) with up to 54 carbon atoms are also very effective. Mixtures of acids can also be used, as can mixtures of any of the types of acids mentioned herein.

In addition to the acids mentioned above, saturated polybasic acids are also useful. In this case, for example azelaic acid (C9, saturated, 2ffi
When using acids such as basicity: HOoC.(CH).C00H), the elongation values for blends are significantly improved and the stiffness is reduced, but the melt index remains almost unchanged.

Furthermore, Cw-Ceo mono- and dicarboxylic acids, and in particular oleic- or polyunsaturated organic acids, including monounsaturated C1e fatty acids), are also very effective.

Cycloalkyl and aromatic carboxylic acids are also useful in the practice of this invention.

Monovalent, divalent and trivalent metal salts of organic acids, especially calcium and zinc salts of fatty acids, are also very effective. Esters and amides of n-acids are also useful.

The number of existing organic acids is enormous. The above example can be carried out without departing from the spirit of the invention and with good results.
Can be replaced by other close analogs.

A more detailed description of organic acids suitable for use in the present invention can be found in U.S. Pat.
Filed on January 15, 1982 (Docket number AD-5199>
can be found inside.

Another group of additives that can be used in the suspended products of the invention are surfactants of the appropriate type. These result in a significant increase in the tensile elongation values of the rod-shaped products.

Effective surfactants are alkanolamides: betaine derivatives; block copolymers consisting of a series of condensates of ethylene oxide with a hydrophobic base produced by condensing propylene oxide and propylene glycol:
Ethoxylated compounds including alcohols, alkylphenols, amines and amides; alkylsulfonates;
Aryl sulfonates, alkyl-arylsulfonates, amine and amidosulfonates, olefin sulfonates, sulfosuccinates, sulfonated fatty acid esters, ethoxylated alkylphenols and oils and sulfonates of fatty acids, naphthalenes and alkylnaphthalene sulfonates, fused naphthalene sulfonates. dodecyl and tridecyl sulfonic acids; alcohols, ethoxylated alcohols, ethoxylated alkylphenols, oils, fatty acids, 5M salts of fatty acid esters, alkaline reel 1iil+
acid salts, and their sodium, ammonium and amine salts; phosphoric acid esters, phosphoric alcohol ethoxylates,
* Phosphorus@ derivatives including acid ether esters xylated, vA acid alkyl acids and vj4u alkyl quaternized; and quaternized surfactants.

The number of existing surfactants is vast. The above examples can be replaced by other close analogs without departing from the spirit of the invention and with good results.

A more detailed description of surfactants suitable for use can be found in US Patent Application No. AD-5201, filed June 19, 1982.

The amount of additives, such as organic acids or surfactants, generally ranges from 0 to about 10% by weight.

Unvulcanized elastomeric polymers are of interest as modified resins for the strip articles of the present invention. They exhibit good compatibility and are useful for obtaining improved flexibility and/or melt strength. When these polymers are used in combination with the ethylene copolymers described above, they may represent from 0 to about 27.5% by weight of the compositions of this invention, preferably up to about 22.5% by weight, most preferably up to about 22.5% by weight. Preferably about 22.5 by weight
Concentrations can range up to %. Styrene-butadiene rubber, polyisobutylene, ethylene/propylene rubber, and ethylene, propylene and diene monomers (
A variety of different rubbers can be used, including terpolymers of EPDM).

Preferred rubbers have an ethylene content of about 20% to about 80% by weight.
% of the ethylene/propylene and EPDMI combination. The diene comonomer is typically methylene norbornene, ethylidene norbornene, dicyclopentadiene, or 1°4-hexadiene, although other dienes can also be used and the concentration of diene is typically 5% by weight. less than The Mooney viscosity is preferably in the range of 20 to 90.

Polymers other than those mentioned above, including both homopolymers and copolymers, may also be used in combination with the above-mentioned polymers to some extent without significantly interfering with the advantages obtainable by the present invention. . These include, but are not limited to, polymers such as ethylene/sulfur dioxide and ethylene/sulfur dioxide.

The formulator may similarly add other ingredients to the strip product of the present invention to achieve some desired effect, such as, for example, lower cost or improved physical properties. Thus, widely used extender resins, waxes, blowing agents, crosslinking agents, antioxidants, etc. can be included in the strip-shaped product of the present invention. Deodorants and/or fragrances may also be included in the leather-like products of the invention to impart a desirable odor, such as a leather odor.

30-A batch blender of industrial size, such as a Banbury or equivalent high-intensity mixer, is perfectly suitable for mixing the components of the present invention. Farrell Continuous Mixer (“FCM”)
) or a continuous mixing device such as a twin-screw extruder are also suitable. In any type of equipment, the dry ingredients are charged in the usual manner. It is often expedient to inject the plasticizer component directly into the mixing chamber of either device, according to methods widely used in these types of devices. If more than one plasticizer is used, and a small amount of any one plasticizer (less than about 10% of the total plasticizer mixture)
If present, the plasticizer must be remixed before being added to the other ingredients of the invention. This promotes uniform dispersion of each plasticizer component in the final composition, thus ensuring optimal properties are achieved. Similarly, since the amount of organic acid used is generally small, often less than 1%, it is important to ensure complete incorporation of the organic acid into the final blend.

If this is not done, highly variable values for the physical properties may result. Thus, it has often been found that it is useful to premix an organic acid into a portion of the sludge; for example, a liquid organic acid may be premixed with a process oil, or a solid organic acid may be premixed with a process oil. It may also be premixed with a portion of the filler. If desired, the copolymer and plasticizer can be premixed in a "master batch" in suitable intensive mixing equipment (e.g. a Banbury mixer or screw extruder). The batch'' can be mixed with fillers and other remaining ingredients to form the final composition. A mixing period of about 3 minutes is generally adequate for Banbury mixers, which normally operate at temperatures between 325 and 375'F. Operating speeds for the FCM system are generally within the prescribed range according to the literature provided by Farrell Corporation of Mansonia, CT. In this case 325-42
A temperature of 5'F is effective. In any case,
At very low plasticizer contents, e.g. about 2-3%, relatively high temperatures are required, whereas about 7%
Plasticizer contents higher than can be mixed well at relatively low temperatures.

It is generally accepted that variations in the order of addition of each component are not critical so long as the final mixture can be completely melted to achieve homogeneity.

After mixing the components, a pellet-like product can be obtained using customary industrial methods, such as cutting and drying the melt under water or dispensing and cutting.

The mixture, either as pellets or as a hot mixture, can be formed into useful products by the divine method directly from the mixing equipment.

For example, it can be formed into a sheet or film using an extruder or calendar, and then punched out to make products such as wallets and handbags. These blends can also be extrusion coated onto woven or nonwoven substrates to provide laminate structures useful as decorative materials, wall coverings, and luggage. It is also possible to obtain laminated structures in which at least one layer of suspended phase parabolites according to the invention is bonded to a rigid and/or soft substrate.

Such substrates can be selected, for example, from the group consisting of woven and non-woven fabrics, scrims, wood, composite paperboards and thermoplastics and heat-effect resins. Other products, such as leather cases and belts, can be injection molded. The surface structure of the molded product can be changed depending on how the material is processed. for example,
A rough, almost fuzzy surface resembling raw natural leather can be produced by simply passing the molten mixture through a two-roll mill. Smooth surfaces in textured leather products can be created by injection molding or extrusion onto polished casting rolls.

Other cosmetic features are influenced by composition. For example, when using suitable wood flour fillers, the color of the finished product can vary from light tan to dark brown, which closely resembles natural leather.

Hard and stiff materials are produced, for example, when a mixture of linear high density polyethylene and ethylene/vinyl acetate copolymer is used as the polymer component, as described above.

Conversely, soft, highly flexible materials can be produced, for example, when ethylene/vinyl acetate copolymers are used as the sole polymeric component.

The following examples are illustrative of the invention. Parts and percentages are by weight unless otherwise indicated.

The composition and physical properties are summarized in Table 1. All formulations were prepared in a Banbury mixer. All ingredients were first mixed in amounts suitable to fill the entire mixing chamber. The chamber was then closed using a ram pressure of 25 psi. The ingredients were mixed for approximately 7 minutes at a continuously adjusted rotor speed to maintain a temperature of 180-185°C.

35- The formulations in Table 1 could be dispensed on a two roll machine after mixing to give sheets with the rough texture of some leather products. The compression molded or injection molded samples had a smooth texture similar to that of a tanned leather product.

All examples have the feel and drape of leather.

Based on flexural modulus and tensile elongation data, formulations containing polyester oil were preferred.

36-1 ψNote (1) EVA copolymer: 18% vinyl acetate, 8% ethylene
2%: Melt index 2.5 (2)'' Brass Train 9796: Polyester oil plasticizer, ■Merry
Industries, Inc. (3)'' Circosol 4240: naphthenic process oil; viscosity 2525 Seibold Universal sec at 100'F: Sun Oil Company (4> No. 9 whiting: calcium carbonate; Josiah Marble Company (5) >Wood flour: Willner #139 wood flour; Willner Wood Products Company (6) Corn meal flour: COB DRI #100;
Frank Miller End Sons, Inc. (7) ASTM 01708.2 inches/min; 0.0
50″ (1,27mm>nominal compression molded plate (8) ASI
I; 4 D790.0.2 in/min; 38-0.050" (1,27 mm) nominal compression molded plate (9
) Full flex wrinkle test: Sample (nominal 0,025″(1
, 27 mm) compression molded plate) is folded sharply back on itself (full flexion). P-Pass, P-=Slight crack at folded edge Patent Applicant: EI DuPont de 39-489-

Claims (1)

Claims: 1. (a) from about 15 to about 55% by weight of ethylene and vinyl esters of saturated carboxylic acids in which the acid moiety has up to 4 carbon atoms; at least one selected from the group consisting of saturated mono- and dicarboxylic acids and esters of said unsaturated acids in which the alcohol moiety has from 1 to 8 carbon atoms, and alpha-olefins containing from 4 to 10 carbon atoms; at least one copolymer with a comonomer, the copolymer having an ethylene content of about 40 to about 95% by weight, and the copolymer having a comonomer content of about 5 to about 60% by weight; The melt index of the copolymer is from about 0.1 to about 150 g/10 min, provided that the copolymer of ethylene is an ethylene/vinyl ester or an ethylene/unsaturated mono- or dicarboxylic acid ester copolymer. In some cases, the copolymer has a weight of about 15
(b) from 1 to about 15% by weight of at least one selected from the group consisting of process oils, epoxidized oils, polyesters, polyethers and polyether esters; Plasticizer; (
C) about 20 to about 70% cellulosic filler by weight;
(d) O to about 10% by weight of an organic acid; ! at least one additive selected from the group consisting of acid derivatives and surfactants; and (61% to about 27.5% by weight)
% of an elastomeric polymer with a hanging appearance. 2. The cellulosic filler contains soft and hard flour, wood 1
JiN, sawdust, corn cob, crushed rice husk,
Claim 1 selected from the group consisting of
Rod-shaped products listed in section. 3. (a) the copolymer of ethylene is present in an amount of about 15 to about 50% by weight; the ethylene content of the copolymer is about 45 to about 90% by weight; The comonomer content is about 10 to about 55% by weight and the melt index of the copolymer is about 0.3 to about 50 (+/10
(h) the plasticizer is present in an amount of about 2 to about 12% by weight; (C) the filler is about 45 to about 70% by weight;
%; and (e) said elastomeric polymer is present in an amount up to about 22.5% by weight. 4. The copolymers of ethylene include ethylene/vinyl acetate, ethylene/acrylic acid, ethylene/methacrylic acid, ethylene/methyl acrylate, ethylene/ethyl acrylate,
Ethylene/isobutyl acrylate, ethylene/n-butyl acrylate, ethylene/isobutyl acrylate/methacrylic acid, ethylene/n-butyl acrylate/acrylic acid, ethylene/isobutyl acrylate/acrylic acid, ethylene/n-butyl acrylate /acrylic acid, ethylene/methyl methacrylate, ethylene/vinyl acetate/methacrylic acid, ethylene/vinyl acetate7/acrylic acid, ethylene, /vinyl acetate/-carbon oxide, ethylene/methyl acrylate/-carbon oxide, ethylene/acrylic n-butyl acid, ・'-carbon oxide, ethylene 7/isobutyl acrylate/-carbon oxide, ethylene/vinyl acetate, monoethyl maleate, ethylene/methyl acrylate/monoethyl maleate, ethylene/butene and ethylene,/octene A molded product according to claim 3 selected from the group consisting of: 5. The shaped product according to claim 4, wherein the filler is selected from the group consisting of soft and hard powders. 6. (a) the copolymer of ethylene is present in an amount of about 15 to about 30% IM; the ethylene content of the copolymer is about 60 to about 85% by weight; the comonomer content is about 15 to about 40% by weight, and the melt index of the copolymer is about 0.7 to about 10M10 minutes; (b) the plasticizer is about 3 to about 8% by weight; and (e) the elastomeric polymer is present in an amount up to about 12% by weight. 7. The copolymer of ethylene is selected from the group consisting of ethylene/vinyl acetate, ethylene/ethyl acrylate, ethylene/methyl acrylate, ethylene/isobutyl acrylate, ethylene/n-butyl acrylate, and ethylene/methyl methacrylate. A shaped product according to claim 6. 8. The shaped product according to claim 1, which is in the form of an extruded sheet or film. 9. The shaped product according to claim 4, which is in the form of an extruded sheet or film. 10. The shaped product according to claim 5, which is in the form of an extruded sheet or film. 11. A shaped product according to claim 7 in the form of an extruded sheet or film. 12. 5- At least one layer bonded to a hard and/or soft substrate Claim 1 l! c! A laminated structure with an early autumn appearance consisting of a soft composition. 1.3. 13. The laminate structure of claim 12, wherein the substrate is selected from the group consisting of woven and non-woven fabrics, scrims, wood, composite paperboard, and thermoplastics and thermosets. 14. The laminated structure according to claim 13, wherein the layer comprises the composition according to claim 4. 15. The laminated structure according to claim 13, wherein the layer comprises the composition according to claim 5. 16. The laminated structure according to claim 13, wherein the Pi layer is made of the composition according to claim 7. 17. The shaped product according to claim 1, which is in the form of an injection molded product. 1B, a molded product according to claim 4 in the form of an injection molded product. 19. The shaped product according to claim 5, which is in the form of an injection molded product. 20. A rod-shaped product according to claims 6 to 7, which is in the form of an injection molded product.